CN113574139A

CN113574139A - Lubricating oil composition and method for producing same

Info

Publication number: CN113574139A
Application number: CN201980094135.XA
Authority: CN
Inventors: 阿部昌太
Original assignee: Mitsui Chemicals Inc
Current assignee: Mitsui Chemicals Inc
Priority date: 2019-03-26
Filing date: 2019-03-26
Publication date: 2021-10-29
Also published as: EP3950894A1; US20220169938A1; EP3950894A4; KR20210139401A; WO2020194542A1

Abstract

The present invention is a lubricating oil composition characterized by comprising (A) a liquid random copolymer of ethylene and an alpha-olefin produced by a specific process, (F) a sulfur-containing compound in which at least one of hydrocarbon groups adjacent to sulfur is a secondary or tertiary hydrocarbon group, and (G) a polymer of an alpha-olefin having 3 to 6 carbon atoms; the lubricating oil composition has a kinematic viscosity at 40 ℃ of 450-51,000 mm²The sulfur content is 0.1 to 5 parts by weight, and the content of the component (G) is 0 to 15 parts by weight. The lubricating oil composition is particularly suitable for gear oils and the like.

Description

Lubricating oil composition and method for producing same

Technical Field

The present invention relates to a lubricating oil composition and a method for producing the same. More specifically, the present invention relates to a lubricating oil composition containing specific components and mainly used for industrial machines and transport machines, and a method for producing the same.

Background

In recent years, environmental problems have attracted much attention worldwide, and one of the corresponding means is as follows: in factories, transportation and management facilities, etc., the power consumption and fuel consumption of industrial machines and transportation machines are reduced. As one of the strategies for solving the above problems, various lubricating oils used in these machines are required to achieve further power saving and fuel saving effects.

Lubricating oil products generally have a so-called temperature dependence of viscosity, that is, when temperature changes, the viscosity changes greatly. Since the use temperature of a machine using a lubricating oil may vary greatly, a lubricating oil having a small temperature dependence of viscosity is considered to be preferable. Therefore, in lubricating oils, in order to reduce the temperature dependence of viscosity, certain polymers soluble in the lubricating oil base may be used as viscosity modifiers. In recent years, α -olefin polymers have been widely used as such viscosity modifiers, and various further improvements have been made in order to further improve the balance of properties of lubricating oils. (patent document 1)

The viscosity index improver as described above is generally used to maintain a suitable viscosity at a high temperature. On the other hand, as part of reducing the environmental load, intensive consideration has recently been given to energy saving and resource saving, and in particular, a viscosity modifier which suppresses an increase in viscosity at low temperatures to a low value (excellent low-temperature characteristics) and is excellent in durability and thermal oxidation resistance stability is required. In general lubricating oil applications, it is advantageous from the economical viewpoint that the concentration of the polymer to be contained is suppressed as low as possible in order to obtain excellent low-temperature characteristics, and for the above-mentioned reasons, a method of using a polymer having a high molecular weight as much as possible is known. However, the α -olefin polymer having a high molecular weight tends to be unfavorable in terms of shear stability.

In industrial lubricating oils, particularly in applications to gear oils, high durability (shear stability) and thermal oxidation resistance stability are required, and performance in consideration of balance with viscosity characteristics is required. Further, among various lubricating oils, gear oils are strongly required to have high performance and long life because they are used under particularly severe conditions, and further improvement of the performance of extreme pressure additives, which are components affecting stable oil film formation, is also desired.

As the lubricant base, mineral oils are classified into groups (I) to (III) of class 3 according to API quality classification, and poly α olefins (PAO) are classified into group (IV) and the others are classified into group (V). In various lubricating oil applications for automobiles, the use rate of group (I) mineral oils, which have been widely used in the past, has been increased to increase the use rate of group (II) and (III) mineral oils or synthetic oils such as polyalphaolefins in order to meet the demand for improved performance and reduced environmental load. On the other hand, the group (III) mineral oils or polyalphaolefins are also used in industrial lubricating oil applications, which require long life and high durability. In particular, in recent years, in industrial gear oils, shear stability is strongly required as a main parameter of durability. The shear stability required above is difficult to be achieved by conventional high molecular weight viscosity modifiers, and α -olefin polymers having a relatively low molecular weight such as polybutene are used. However, depending on the application, there is room for improvement in the viscosity characteristics of polybutene, particularly in sufficient fluidity at low temperatures.

Documents of the prior art

Patent document

Patent document 1: international publication No. 00/34420 pamphlet

Disclosure of Invention

Problems to be solved by the invention

The extreme pressure additive is a component that chemically reacts with a material forming a friction surface of a machine or the like to form a pressure-resistant coating on the friction surface, for example. The materials of these friction surfaces are mostly metals, and thus extreme pressure additives tend to form highly polar components

On the other hand, synthetic oils such as polyalphaolefins often have a low polarity as base oils, and therefore, in particular, in the industrial gear oil application requiring a high viscosity, the extreme pressure additives having a high polarity have a problem of poor compatibility.

Accordingly, an object of the present invention is to provide an industrial lubricating oil which is excellent in compatibility with an extreme pressure additive, has an excellent balance between viscosity characteristics and shear stability, and is also excellent in durability and thermal oxidation resistance stability.

Means for solving the problems

Under such circumstances, the present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by using an ethylene/α -olefin copolymer produced using a specific catalyst and optionally 1 or more kinds of synthetic oils and/or mineral oils having specific viscosities, viscosity indexes, and pour points as base agents and combining a specific extreme pressure additive with the base agents, and have completed the present invention.

Specific examples of the present invention include the following embodiments.

[1] A lubricating oil composition characterized by containing the following (A) and (F) and optionally (G),

(A) a liquid random copolymer of ethylene and an alpha-olefin produced by the process (alpha) below,

(F) a sulfur-containing compound in which at least one of the hydrocarbon groups adjacent to sulfur is a secondary hydrocarbon group or a tertiary hydrocarbon group,

(G) a polymer of an alpha-olefin having 3 to 6 carbon atoms,

the lubricating oil composition has a kinematic viscosity at 40 ℃ of 450-51,000 mm²/s，

The sulfur content is 0.1 to 5 parts by weight.

(wherein the total amount of the lubricating oil composition is 100 parts by weight.)

(method (. alpha.))

A process (alpha) for producing a liquid random copolymer of ethylene and an alpha-olefin, which comprises the step of solution-polymerizing ethylene and an alpha-olefin having 3 to 20 carbon atoms in the presence of a catalyst system comprising the following components (a) and (b),

(a) a crosslinked metallocene compound represented by the following formula 1,

(b) at least one compound selected from the group consisting of the following (i) and (ii),

(i) an organoaluminum oxy-compound which is a compound of an organoaluminum oxy-compound,

(ii) a compound which reacts with the above-mentioned crosslinked metallocene compound to form an ion pair.

[ chemical formula 1]

[ in formula 1, R¹、R²、R³、R⁴、R⁵、R⁸、R⁹And R¹²Each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, adjacent groups being optionally linked to each other to form a ring structure,

R⁶and R¹¹Are identical to each other and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group,

R⁷and R¹⁰Are identical to each other and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group,

R⁶and R⁷Optionally bonding with hydrocarbon with 2-3 carbon atoms to form a ring structure,

R¹¹and R¹⁰Optionally bonding with hydrocarbon with 2-3 carbon atoms to form a ring structure,

R⁶、R⁷、R¹⁰and R¹¹Not being hydrogen atoms at the same time;

y is a carbon atom or a silicon atom;

R¹³and R¹⁴Independently is an aryl group;

m is Ti, Zr or Hf;

q is independently a halogen, a hydrocarbyl group, an anionic ligand, or a neutral ligand capable of coordinating to a lone pair of electrons;

j is an integer of 1 to 4. Angle (c)

[2]Such as [1]]The lubricating oil composition, wherein a substituent (R) bonded to the cyclopentadienyl group of the metallocene compound represented by the above formula 1¹、R²、R³And R⁴) At least 1 of them is a hydrocarbon group having 4 or more carbon atoms.

[3]Such as [1]]Or [2]]The lubricating oil composition described in (1), wherein R⁶And R¹¹The same applies to the hydrocarbyl group with 1-20 carbon atoms.

[4]Such as [1]]～[3]The lubricating oil composition according to any one of the above formulas 1, wherein a substituent (R) is bonded to the 3-position of the cyclopentadienyl group of the metallocene compound²Or R³) Is a hydrocarbyl group.

[5]Such as [4]]The lubricating oil composition, wherein a hydrocarbon group (R) is bonded to the 3-position of the cyclopentadienyl group of the metallocene compound represented by the above formula 1²Or R³) Is n-butyl.

[6]Such as [1]]～[5]The lubricating oil composition according to any one of the above formulas (1), wherein the substituent (R) is bonded to the 2-position and the 7-position of the fluorenyl group of the metallocene compound⁶And R¹¹) Are all tert-butyl.

[7] The lubricating oil composition according to any one of [1] to [6], wherein the compound that forms an ion pair by reacting with the crosslinked metallocene compound is a compound represented by the following formula 6.

[ chemical formula 2]

[ in formula 6, R^e+Is H⁺A carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatriene cation, or a ferrocenium cation with a transition metal, R^f～RⁱEach independentlyIs a hydrocarbon group having 1 to 20 carbon atoms. Angle (c)

[8] The lubricating oil composition according to [7], wherein the ammonium cation is a dimethylanilinium cation.

[9] The lubricating oil composition according to [7] or [8], wherein the above catalyst system further comprises an organoaluminum compound selected from the group consisting of trimethylaluminum and triisobutylaluminum.

[10] The lubricating oil composition according to any one of [1] to [9], further comprising a component (B) satisfying all of the following requirements (B-1) to (B-3).

(B-1) kinematic viscosity at 100 ℃ of 3 to 120mm²(ii) a ratio of (c) to(s) below,

(B-2) a viscosity index of 90 or more,

(B-3) a pour point of-10 ℃ or lower.

[11] The lubricating oil composition according to [10], wherein the component (B) is a synthetic oil (C) satisfying all of the following requirements (C-1) to (C-3).

(C-1) a kinematic viscosity at 100 ℃ of 20 to 120mm²/s，

(C-2) a viscosity index of 120 or more,

(C-3) a pour point of-30 ℃ or lower.

[12] The lubricating oil composition according to [10], wherein the component (B) is a synthetic oil (D) satisfying all of the following requirements (D-1) to (D-3).

(D-1) kinematic viscosity at 100 ℃ of 3-10 mm²/s，

(D-2) a viscosity index of 120 or more,

(D-3) a pour point of-40 ℃ or lower.

[13] The lubricating oil composition according to [10], wherein the component (B) is a mineral oil (E) satisfying all of the following requirements (E-1) to (E-3).

(E-1) kinematic viscosity at 100 ℃ of 3 to 40mm²/s，

(E-2) a viscosity index of 90 or more,

(E-3) a pour point of-10 ℃ or lower.

[14] The lubricating oil composition according to [11] or [12], wherein the component (C) and/or the component (D) is a synthetic oil containing an alpha-olefin polymer and/or ester compound having 8 to 20 carbon atoms.

[15] The lubricating oil composition according to [13], wherein the component (E) is 1 or more mineral oils selected from the group (I), (II) and (III) of API quality classification.

[16] The lubricating oil composition according to [10], wherein the component (B) is at least 1 selected from the group consisting of a synthetic oil (C) satisfying all of the following requirements (C-1) to (C-3), a synthetic oil (D) satisfying all of the following requirements (D-1) to (D-3), and a mineral oil (E) satisfying all of the following requirements (E-1) to (E-3),

the saturated hydrocarbon content is 80 wt% or more with respect to the total amount of the components (A) to (E).

(C-1) a kinematic viscosity at 100 ℃ of 20 to 120mm²/s，

(C-2) a viscosity index of 120 or more,

(C-3) a pour point of-30 ℃ or lower,

(D-1) kinematic viscosity at 100 ℃ of 3-10 mm²/s

(D-2) a viscosity index of 120 or more,

(D-3) pour point of-40 ℃ or lower

(E-1) kinematic viscosity at 100 ℃ of 3 to 40mm²/s

(E-2) a viscosity index of 90 or more,

(E-3) a pour point of-10 ℃ or lower.

[17] A lubricating oil composition comprising a liquid random copolymer of ethylene and an alpha-olefin, (F) a sulfur-containing compound wherein at least one of the hydrocarbon groups adjacent to sulfur is a secondary or tertiary hydrocarbon group, and optionally (G) a polymer of an alpha-olefin having 3 to 6 carbon atoms,

the liquid random copolymer of ethylene and an alpha-olefin satisfies all of the following requirements (A-1) to (A-5),

(A-1) contains 40 to 60 mol% of an ethylene unit and 60 to 40 mol% of an alpha-olefin unit having 3 to 20 carbon atoms,

(A-2) has a number average molecular weight (Mn) of 500 to 10,000 and a molecular weight distribution (Mw/Mn, Mw is a weight average molecular weight) of 3 or less as measured by Gel Permeation Chromatography (GPC),

(A-3) has a thickness of 30 to 5,000mm²A kinematic viscosity at 100 ℃ in/s,

(A-4) has a pour point of 30 to-45 ℃,

(A-5) has a bromine number of 0.1g/100g or less,

the lubricating oil composition has a kinematic viscosity at 40 ℃ of 962-4570 mm²/s，

The sulfur content is 0.1 to 5 parts by weight.

[18] The lubricating oil composition according to any one of [1] to [17], wherein the lubricating oil composition is a gear oil composition.

[19] A method for producing a lubricating oil composition, comprising the steps of:

a step of producing (A) a liquid random copolymer of ethylene and an α -olefin by the following method (α); and

the liquid random copolymer (A), a sulfur-containing compound (F) in which at least one of the hydrocarbon groups adjacent to sulfur is a secondary or tertiary hydrocarbon group, a component (B) satisfying all of the requirements (B-1) to (B-3) below, and an optional component (G) a polymer of an alpha-olefin having 3 to 6 carbon atoms are mixed to produce a mixture having a kinematic viscosity at 40 ℃ of 450 to 51,000mm²A step of preparing a lubricating oil composition having a sulfur content of 0.1 to 5 parts by weight.

(method (. alpha.))

(a) a crosslinked metallocene compound represented by the following formula 1,

[ chemical formula 3]

R⁶、R⁷、R¹⁰and R¹¹Not being hydrogen atoms at the same time;

y is a carbon atom or a silicon atom;

R¹³and R¹⁴Independently is an aryl group;

m is Ti, Zr or Hf;

j is an integer of 1 to 4. Angle (c)

ADVANTAGEOUS EFFECTS OF INVENTION

The lubricating oil composition of the present invention is excellent in durability and thermal oxidation resistance stability, because it is excellent in compatibility, i.e., it is a liquid state having excellent transparency, and is excellent in viscosity characteristics and shear stability, even when it contains a sulfur compound which is considered to be suitable as an extreme pressure additive. Therefore, the lubricating oil is suitable for industrial lubricating oil, especially gear oil.

Detailed Description

The lubricating oil composition of the present invention is characterized by comprising a liquid random copolymer of ethylene and an α -olefin (also referred to as "ethylene/α -olefin copolymer (a)" in the present specification) produced by the following method (α) and a sulfur compound (F) satisfying specific requirements. Hereinafter, each component will be described.

[ ethylene-alpha-olefin copolymer (A) ]

The ethylene/α -olefin copolymer (a) in the present invention is a liquid random copolymer of ethylene and α -olefin produced by the following process (α).

(method (. alpha.))

(a) a crosslinked metallocene compound represented by the following formula 1,

[ chemical formula 4]

R⁷and R¹⁰Identical to each other, is a hydrogen atom, a hydrocarbon group or a silicon-containingA hydrocarbon group,

R⁶、R⁷、R¹⁰and R¹¹Not being hydrogen atoms at the same time;

y is a carbon atom or a silicon atom;

R¹³and R¹⁴Independently is an aryl group;

m is Ti, Zr or Hf;

q is independently a halogen, a hydrocarbyl group, an anionic ligand, or a neutral ligand that can coordinate a lone pair of electrons;

j is an integer of 1 to 4. Angle (c)

Wherein the hydrocarbon group has 1 to 20, preferably 1 to 15, and more preferably 4 to 10 carbon atoms, and means, for example, an alkyl group, an aryl group, or the like, and the aryl group has 6 to 20, preferably 6 to 15 carbon atoms.

Examples of the silicon-containing hydrocarbon group include an alkyl group or an aryl group having 3 to 20 carbon atoms and containing 1 to 4 silicon atoms, and more specifically, a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and the like.

In the crosslinked metallocene compound represented by formula 1, the cyclopentadienyl group may be substituted or unsubstituted.

In the crosslinked metallocene compound represented by the formula 1,

(i) substituents bonded to cyclopentadienyl (R) are preferred¹、R²、R³And R⁴) At least one of which is a hydrocarbon group,

(ii) more preferred is a substituent (R)¹、R²、R³And R⁴) At least one of which is a hydrocarbon group having 4 or more carbon atoms,

(iii) most preferred is a substituent (R) bonded to the 3-position of the cyclopentadienyl group²Or R³) A hydrocarbon group having 4 or more carbon atoms (e.g., n-butyl group).

R¹、R²、R³And R⁴When at least 2 of them are substituents (i.e., not hydrogen atoms), the substituents may be the same or different, and at least 1 of them is preferably a hydrocarbon group having 4 or more carbon atoms.

In the metallocene compound represented by the formula 1, R bonded to a fluorenyl group⁶And R¹¹Same as R⁷And R¹⁰Same, except that R⁶、R⁷、R¹⁰And R¹¹Not simultaneously hydrogen atoms. In the high-temperature solution polymerization of polyalphaolefin, R is preferably used for improving the polymerization activity⁶And R¹¹Are not hydrogen atoms, more preferably R⁶、R⁷、R¹⁰And R¹¹Are not hydrogen atoms. For example, R bonded to the 2-and 7-positions of the fluorenyl group⁶And R¹¹The same hydrocarbon group of 1 to 20 carbon atoms, preferably all tertiary butyl, R⁷And R¹⁰The hydrocarbon group is the same hydrocarbon group having 1 to 20 carbon atoms, and preferably all of the hydrocarbon groups are t-butyl groups.

The main chain portion (linkage, Y) linking the cyclopentadienyl group and the fluorenyl group is a bridging portion of 2 covalent bonds containing 1 carbon atom or silicon atom as a structural bridging portion imparting stereorigidity to the above-mentioned crosslinked metallocene compound represented by formula 1. The bridging atom (Y) in the bridge has 2 aryl groups (R) which may be the same or different¹³And R¹⁴). Therefore, the cyclopentadienyl group and the fluorenyl group are bonded through a bridging portion of a covalent bond containing an aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, and a substituted aryl group in which 1 or more aromatic hydrogens (sp) of the phenyl group, naphthyl group or anthracenyl group are substituted with a substituent²Type hydrogen) to form a substituted group. ). Examples of the substituent of the substituted aryl group include a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and the like, and a phenyl group is preferable. Among the above-mentioned crosslinked metallocene compounds represented by the formula 1, R is preferred from the viewpoint of ease of production¹³And R¹⁴The same is true.

In the crosslinked metallocene compound represented by the formula 1, Q is preferably a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and examples of the hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,2, 2-tetramethylpropyl, sec-butyl, tert-butyl, 1-dimethylbutyl, 1, 3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl and 1-methyl-1-cyclohexyl. When j is an integer of 2 or more, Q may be the same or different.

Examples of the crosslinked metallocene compound (a) include:

ethylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-tert-butyl-5-methylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, ethylene [ eta ] ethylene⁵- (3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethylene⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethyl acetate⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Ethylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-tert-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-tert-butylcyclopentadienyl)](benzofluorenyl group)Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethylene⁵- (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethyl acetate⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Ethylene [ eta ]⁵- (3-n-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-n-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] or⁵- (3-n-butylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, ethylene [ eta ] ethylene⁵- (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethylene⁵- (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, ethylene [ eta ] ethyl acetate⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, ethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] s⁵- (3-tert-butyl-5-methylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadieneBase)](dibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [. eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] s⁵- (3-tert-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [. eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Diphenylmethylene [ eta ] s⁵- (3-n-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-n-butylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, bisPhenylmethylene [ eta ] or⁵- (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, diphenylmethylene [ eta ]⁵- (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, diphenylmethylene [. eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, diphenylmethylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] was⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butyl-5-methylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-tert-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride,Di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ]⁵- (3-tert-butylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-tert-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] was⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-tert-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride,

Di (p-tolyl) methylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)](η⁵-fluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-n-butylcyclopentadienyl)][η⁵- (3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-di-tert-butylfluorenyl)]Zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ]⁵- (3-n-butylcyclopentadienyl)](benzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] methyl⁵- (3-n-butylcyclopentadienyl)](dibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta. ]⁵- (3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] was⁵- (3-n-butylcyclopentadienyl)](2, 7-Diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene [ eta ] was⁵- (3-n-butylcyclopentadienyl)][η⁵- (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl)]Zirconium dichloride, and the like.

Examples of the crosslinked metallocene compound (a) include, but are not limited to, compounds obtained by replacing a zirconium atom with a hafnium atom, compounds obtained by replacing a chlorine ligand with a methyl group, and the like.

As the organoaluminum oxy-compound used in the catalyst system of the present invention, conventional aluminoxane can be used. For example, linear or cyclic aluminoxane represented by the following formulas 2 to 5 can be used. The organoaluminum oxy-compound may contain a small amount of an organoaluminum compound.

[ chemical formula 5]

In the formulas 2-4, R is independently a hydrocarbon group having 1-10 carbon atoms, Rx is independently a hydrocarbon group having 2-20 carbon atoms, and m and n are independently an integer of 2 or more, preferably 3 or more, more preferably 10-70, and most preferably 10-50.

[ chemical formula 6]

In the formula 5, R^cIs a hydrocarbon group of 1 to 10 carbon atoms, R^dIndependently a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

In formula 2 or formula 3, R is the methyl group (Me) of the organoaluminum oxy-compound which has been conventionally referred to as "methylaluminoxane".

The above-mentioned methylaluminoxane is easily available and has high polymerization activity, and thus is generally used as an active agent in polyolefin polymerization. However, methylaluminoxane is difficult to dissolve in saturated hydrocarbons, and therefore, it is used as a solution of an aromatic hydrocarbon such as toluene or benzene, which is not environmentally friendly. Therefore, in recent years, as aluminoxane dissolved in saturated hydrocarbon, a flexible body (flexible body) of methylaluminoxane represented by formula 4 has been developed and used. The modified methylaluminoxane represented by formula 4 is produced by using trimethylaluminum and an alkylaluminum other than trimethylaluminum, for example, trimethylaluminum and triisobutylaluminum, as described in U.S. Pat. No. 4960878 and U.S. Pat. No. 5041584. Alumoxanes with Rx being isobutyl are commercially available as saturated hydrocarbon solutions under the trade names MMAO, TMAO. (see Tosoh Finechem Corporation, Tosoh Research & Technology Review, Vol 47, 55 (2003)).

As the compound (ii) contained in the catalyst system, which reacts with the crosslinked metallocene compound to form an ion pair, (hereinafter, referred to as "ionic compound" as needed), a Lewis acid, an ionic compound, borane, a borane compound, and a carborane compound can be used, and these are described in Korean patent No. 10-0551147, Japanese patent laid-open No. 1-501950, Japanese patent laid-open No. 3-179005, Japanese patent laid-open No. 3-179006, Japanese patent laid-open No. 3-207703, Japanese patent laid-open No. 3-207704, and U.S. Pat. No. 5321106. If necessary, heteropoly compounds, isopoly compounds, etc. can be used, and ionic compounds described in Japanese patent application laid-open No. 2004-51676 can be used. The ionic compounds may be used singly or in combination of two or more. More specifically, BR is an example of a lewis acid₃Examples of the compound represented by (R) include fluoride, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (e.g., methyl group), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (e.g., phenyl group), and the like), and boron trifluoride, triphenylboron, tris (4-fluorophenyl) boron, tris (3, 5-difluorophenyl) boron, tris (4-fluorophenyl) boron, tris (pentafluorophenyl) boron, and tris (p-tolyl) boron. When the ionic compound is used, the amount of the compound used and the amount of sludge generated are smaller than those of the organoaluminum oxy-compound, and therefore, it is economically advantageous. In the present invention, the ionic compound is preferably a compound represented by the following formula 6.

[ chemical formula 7]

In the formula 6, R^e+Is H⁺A carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatriene cation, or a ferrocenium cation with a transition metal, R^f～RⁱEach independently is an organic group, preferably a hydrocarbyl group having 1 to 20 carbon atoms, more preferably an aryl group, for example, a pentafluorophenyl group. Examples of the carbonium cation include a tris (methylphenyl) carbonium cation, a tris (dimethylphenyl) carbonium cation, and the like, and examples of the ammonium cation include a dimethylanilinium cation, and the like.

The compound represented by the above formula 6 preferably includes N, N-dialkylanilinium salts, and specifically includes N, N-dimethylanilinium tetraphenylborate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-diethylanilinium tetraphenylborate, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N-diethylanilinium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, N-2,4, 6-pentamethylanilinium tetraphenylborate, N-2,4, 6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, and the like.

The catalyst system used in the present invention further contains (c) an organoaluminum compound, if necessary. The organoaluminum compound functions to activate the crosslinked metallocene compound, the organoaluminum oxy-compound, the ionic compound, and the like. As the organoaluminum compound, organoaluminum represented by the following formula 7 and an alkyl complex of a group 1 metal represented by the following formula 8 and aluminum can be preferably used.

R^a _mAl(OR^b)_nH_pX_q… (formula 7)

In the formula 7, R^aAnd R^bEach independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, and m is 0<m is an integer of not more than 3, n is an integer of not less than 0 and not more than n is not more than 3, and p is 0<p is an integer of not more than 3, q is not less than 0 and not more than q<3, m + n + p + q is 3.

M²AlR^a ₄… (formula 8)

In formula 8, M²Represents Li, Na or K, R^aIs a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.

As examples of the organoaluminum compound represented by formula 7, there can be mentioned readily available organoaluminum compoundsAnd trimethyl aluminum, triisobutyl aluminum and the like are obtained. Examples of the alkyl complex compound of the group 1 metal represented by formula 8 and aluminum include LiAl (C)₂H₅)₄、LiAl(C₇H₁₅)₄And the like. A compound similar to the compound represented by formula 7 may be used. For example, a catalyst such as (C) can be used₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂Thus, at least 2 aluminum compounds are bonded to each other through a nitrogen atom.

In the method for producing the ethylene- α -olefin copolymer (C), the amount of the crosslinked metallocene compound (a) represented by the formula 1 is preferably 5 to 50% by weight with respect to the entire catalyst composition. Further, it is preferable that (b) (i) the amount of the organoaluminum oxy-compound is 50 to 500 equivalents based on the number of moles of the crosslinked metallocene compound used, (b) (ii) the amount of the compound which reacts with the crosslinked metallocene compound to form an ion pair is 1 to 5 equivalents based on the number of moles of the crosslinked metallocene compound used, and (c) the amount of the organoaluminum compound is 5 to 100 equivalents based on the number of moles of the crosslinked metallocene compound used.

The catalyst system used in the present invention may have, for example, the following [1] to [4 ].

[1] (a) a crosslinked metallocene compound represented by the formula 1, and (b) (i) an organoaluminum oxy-compound

[2] A crosslinked metallocene compound represented by the formula 1, (b) (i) an organoaluminum oxy-compound, and (c) an organoaluminum compound.

[3] The metallocene catalyst comprises (a) a bridged metallocene compound represented by the formula 1, (b) (ii) a compound which reacts with the bridged metallocene compound to form an ion pair, and (c) an organoaluminum compound.

[4] A crosslinked metallocene compound represented by the formula 1, and (b) an organoaluminum oxy-compound, and (ii) a compound which reacts with the crosslinked metallocene compound to form an ion pair.

(a) The crosslinked metallocene compound represented by formula 1 (component (a)), (b) (i) the organoaluminum oxy-compound (component (b)), (ii) the compound which reacts with the crosslinked metallocene compound to form an ion pair, and/or (c) the organoaluminum compound (component (c)) may be introduced in an arbitrary order with respect to the starting material monomer (a mixture of ethylene and an α -olefin having 3 to 20 carbon atoms). For example, the components (a), (b) and/or (c) are introduced into a polymerization reactor filled with a raw material monomer, either individually or in any order. Alternatively, at least 2 of the components (a), (b) and/or (c) may be mixed as necessary, and then the mixed catalyst composition may be introduced into a polymerization reactor filled with a raw material monomer.

The ethylene-alpha-olefin copolymer (C) is produced by solution polymerization of ethylene and an alpha-olefin having 3 to 20 carbon atoms in the presence of the catalyst system. The alpha-olefin having 3 to 20 carbon atoms may be at least 1 of a linear alpha-olefin such as propylene, 1-butene, 1-pentene, 1-hexene, etc., a branched alpha-olefin such as isobutylene, 3-methyl-1-butene, 4-methyl-1-pentene, etc., and a mixture thereof. Preferably, 1 or more kinds of alpha-olefins having 3 to 6 carbon atoms are used, and more preferably, propylene is used. The solution polymerization can be carried out by using an inert solvent such as propane, butane or hexane, or an olefin monomer itself as a medium. In the copolymerization of ethylene and alpha-olefin of the present invention, the temperature of the copolymerization is usually 80 to 150 ℃ and preferably 90 to 120 ℃ and the pressure of the copolymerization is usually atmospheric pressure to 500kgf/cm²Preferably from atmospheric pressure to 50kgf/cm²These may vary depending on the reaction materials, reaction conditions, and the like.

The polymerization can be carried out batchwise, semicontinuously or continuously, preferably continuously.

The ethylene- α -olefin copolymer (C) is in a liquid phase at room temperature and has a structure in which α -olefin units are uniformly distributed in the copolymer chain. The ethylene-alpha-olefin copolymer (C) contains, for example, 60 to 40 mol% (preferably 45 to 55 mol%) of ethylene units derived from ethylene, and, for example, 40 to 60 mol% (preferably 45 to 55 mol%) of alpha-olefin units having 3 to 20 carbon atoms derived from an alpha-olefin having 3 to 20 carbon atoms.

The ethylene-alpha-olefin copolymer (C) has a number average molecular weight (Mn) of, for example, 500 to 10,000, preferably 800 to 6,000, and a molecular weight distribution (Mw/Mn, Mw being a weight average molecular weight) of, for example, 3 or less, preferably 2 or less. The number average molecular weight (Mn) and molecular weight distribution (Mw/Mn) were determined by Gel Permeation Chromatography (GPC).

The ethylene-alpha-olefin copolymer (A) has a thickness of, for example, 30 to 5,000mm, preferably 50 to 3,000mm²A kinematic viscosity at 100 ℃ of per second, for example, a pour point of from 30 to-45 ℃, preferably from 20 to-35 ℃, for example, a bromine number of 0.1g/100g or less.

The crosslinked metallocene compound represented by formula 1 has high polymerization activity particularly for copolymerization of ethylene and α -olefin, and by using the crosslinked metallocene compound, polymerization is selectively stopped by introducing hydrogen into a molecular terminal, and thus the unsaturated bond of the obtained ethylene- α -olefin copolymer (a) is reduced. In addition, the ethylene- α -olefin copolymer (a) has a controlled molecular weight distribution because of its high random copolymerizability, and is excellent in shear stability and viscosity characteristics.

Therefore, the lubricating oil composition containing the ethylene/α -olefin copolymer used in the present invention is excellent in the balance between viscosity characteristics and shear stability, and is excellent in durability and thermal oxidation resistance stability.

[ lubricating oil base Material ]

In the present invention, other lubricating oil materials may be used as necessary. It is preferable to use the component (B) satisfying all of the following requirements (B-1) to (B-3).

(B-1) kinematic viscosity at 100 ℃ of 3 to 120mm²Preferably 4 to 110 mm/s²/s，

(B-2) a viscosity index of 90 or more, preferably 95 or more,

(B-3) a pour point of-10 ℃ or lower, preferably-15 ℃ or lower.

The component (B) is a component other than the ethylene/alpha-olefin copolymer (A) and the alpha-olefin polymer (G) having 3 to 6 carbon atoms.

Preferable examples of such a lubricating oil material include synthetic oils and mineral oils such as the following components (C) to (E).

The mineral oil (E) used as required in the present invention is known as a so-called lubricant base material. The lubricating oil base materials are specified by API (American Petroleum institute) classification and classified into groups. The properties of the lubricating base material are shown in table 1.

Mineral oils used as lubricating base materials are generally subjected to a purification step such as dewaxing, and are composed of three grades according to the purification method.

[ Table 1]

1, 1: measured according to ASTM D445(JIS K2283)

A, 2: measured according to ASTM D3238

3, a: measured according to ASTM D4294(JIS K2541)

4, v: mineral oils having a content of saturated hydrocarbons of less than 90 (vol%) and a content of sulfur of less than 0.03 wt%, or a content of saturated hydrocarbons of 90 (vol%) or more and a content of sulfur of more than 0.03 wt% are included in group (I)

The mineral oil (E) has the following characteristics (E-1) to (E-3), and is preferably a high-viscosity index mineral oil which belongs to groups (I) to (III) of the API quality classification (preferably belongs to group (III)) and is purified by a hydrogenolysis method or the like.

(E-1) kinematic viscosity at 100 ℃ of 3 to 40mm²Preferably 5 to 35 mm/s²/s，

(E-2) a viscosity index of 90 or more, preferably 95 or more,

(E-3) a pour point of-10 ℃ or lower, preferably-15 ℃ or lower.

The synthetic oil (D) used in the present invention has the following characteristics (D-1) to (D-3), and preferably low viscosity Polyalphaolefin (PAO) and/or polyol ester, fatty acid ester, or the like.

(D-1) kinematic viscosity at 100 ℃ of 3-10 mm²Preferably 4 to 8 mm/s²/s，

(D-2) a viscosity index of 120 or more, preferably 125 or more,

(D-3) a pour point of-40 ℃ or lower, preferably-50 ℃ or lower.

The Polyalphaolefin (PAO) belonging to group (IV) in table 1 is a hydrocarbon polymer obtained by polymerizing an α -olefin having at least 8 carbon atoms as a raw material monomer, and for example, polydecene obtained by polymerizing 1-decene is exemplified. Such polyalphaolefins are further preferred embodiments of the synthetic oil (D).

Such an α -olefin oligomer can be produced by cationic polymerization, thermal polymerization, or radical polymerization using a ziegler catalyst or a lewis acid as a catalyst. Of course, the catalyst can also be obtained by polymerizing the corresponding olefin in the presence of the catalyst described in the above-mentioned patent document 1.

As the base oil belonging to group (V) in table 1, alkylbenzenes, alkylnaphthalenes, ester oils, and the like can be exemplified.

Alkylbenzenes and alkylnaphthalenes are usually produced by Friedel-crafts alkylation of benzene or naphthalene with an olefin, and most of the alkylbenzenes and alkylnaphthalenes are dialkylbenzenes or dialkylnaphthalenes having an alkyl chain length of 6 to 14 carbon atoms. The alkylated olefin used in the manufacture of the alkylbenzene or alkylnaphthalene may be a straight or branched chain olefin or a combination thereof. The above-mentioned production method is described in, for example, U.S. Pat. No. 3909432.

Examples of the ester include: monoesters made from monobasic acids and alcohols; diesters made from dibasic acids and alcohols, or diesters made from dihydric alcohols and monobasic acids or acid mixtures; polyol esters produced by reacting diols, triols (e.g., trimethylolpropane), tetraols (e.g., pentaerythritol), hexaols (e.g., dipentaerythritol), and the like with a monobasic acid or acid mixture; and so on. Examples of these esters include tridecyl nonanoate, di (2-ethylhexyl) adipate, di (2-ethylhexyl) azelate, trimethylolpropane triheptanoate, pentaerythritol tetraheptanoate, and the like.

The synthetic oil (C) used as required in the present invention preferably satisfies the following characteristics (C-1) to (C-3) and is preferably a Polyalphaolefin (PAO) belonging to group (IV), but may contain a synthetic oil such as an ester belonging to group (V).

(C-1) a kinematic viscosity at 100 ℃ of 20 to 120mm²Preferably 30 to 110mm in terms of the mass fraction of the particles²/s，

(C-2) a viscosity index of 120 or more, preferably 130 or more,

the pour point of (C-3) is-30 ℃ or lower, preferably-35 ℃ or lower.

The component (B) suitable for use as the low-viscosity lubricating base material in the present invention contains 1 or more components selected from the group consisting of synthetic oil (C), synthetic oil (D) and mineral oil (E), and may be1 or 2 or more of each of synthetic oil (C), synthetic oil (D) and mineral oil (E), or may be a mixture of synthetic oil (C) or synthetic oil (D) and mineral oil (E).

When the sum of the ethylene/α -olefin copolymer (a) and the sulfur compound (F) described later is taken as 100 parts by weight, the above-mentioned components (B) to (E) can be used in a proportion of preferably 2 to 80 parts by weight, more preferably 3 to 60 parts by weight, and particularly preferably 4 to 40 parts by weight.

In the lubricating oil composition of the present invention, the saturated hydrocarbon content is preferably 80% by weight or more based on the total amount of the hydrocarbon components of the components (a) to (E). More preferably 90% or more, still more preferably 95% or more, and particularly preferably 96% or more.

If the saturated hydrocarbon ratio is too low, the durability as a lubricating oil may be insufficient.

The α -olefin polymer (G) having 3 to 6 carbon atoms, which is used as needed in the present invention, is an α -olefin polymer having a structural unit of an α -olefin selected from α -olefins having 3 to 6 carbon atoms of more than 70 mol%, and is 15 parts by weight or less, preferably 12 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less, and particularly preferably 2 parts by weight or less, based on 100 parts by weight of the total amount of the lubricating oil composition. The preferred lower limit is 0 part by weight.

When the content of the alpha-olefin polymer (G) having 3 to 6 carbon atoms is too high, the shear viscosity may decrease with time.

[ Sulfur Compound (F) ]

The sulfur compound (F) used in the present invention is characterized in that the carbon atom adjacent to sulfur is a secondary carbon or a tertiary carbon. Examples of the substituent containing such a carbon include isopropyl (i-Pr), sec-butyl (s-Bu), tert-butyl (t-Bu), 2-hexyl, 3-hexyl, 2-methyl-2-pentyl and 3-methyl-3-pentyl.

The sulfur compound (F) having a substituent having such a structure is generally used as an extreme pressure additive, and surprisingly, although it maintains strong polarity, it has high compatibility with the ethylene/α -olefin copolymer (a) and can form a lubricating oil composition having excellent transparency. In addition, the sulfur compound (F) tends to be as follows: even when the viscosity of each oil agent is high, compatibility is not easily impaired, and a product having high transparency can be easily obtained as a lubricating oil composition described later. The simultaneous achievement of the above compatibility and polarity is considered to be brought about by the above-mentioned structure containing a bulky hydrocarbon substituent.

The sulfur compound (F) used in the present invention preferably has an atomic ratio of carbon to sulfur of 1.5 to 20, more preferably 1.8 to 15, and particularly preferably 2 to 10. Since the sulfur compound satisfying such a range has a strong polarity, it is considered that the sulfur compound strongly interacts with the surface of a gear of a metal machine or the like, for example, and a strong coating film can be formed.

When the atomic ratio is too high, the polarity may be insufficient, while when the atomic ratio is too low, the compatibility with the ethylene/α -olefin copolymer (a) may be reduced.

The sulfur compound as described above is preferably a compound having a structure in which hydrocarbon substituents having the above-described secondary or tertiary hydrocarbon structure are present at both ends of the sulfur chain. Examples thereof include t-Bu2-S, S-Bu2-S, i-Pr2-S, t-Bu-S-S-t-Bu, S-Bu-S-S-S-Bu, i-Pr-S-S-i-Pr, t-Bu-S-S-S-t-Bu, S-Bu-S-S-S-S-Bu, i-Pr-S-S-S-i-Pr, t-Bu-S-S-S-S-t-Bu, S-Bu-S-S-S-S-S-Bu, i-Pr-S-S-S-S-i-Pr, and the like. (wherein Bu represents a butyl group, Pr represents a propyl group, S-represents a secondary (secondary), and t-represents a tertiary (tertiary), S is sulfur, of course.)

The lubricating oil composition of the present invention has a sulfur content of 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 1 to 3 parts by weight, based on 100 parts by weight of the total amount of the lubricating oil composition.

When the above range is satisfied, the film is transparent and can simultaneously realize the lubricating performance such as film formation at a high level. If the content of sulfur is too low, the lubricating oil performance may be insufficient, and if the content of sulfur is too high, the transparency as a lubricating oil may be impaired.

[ lubricating oil composition ]

The lubricating oil composition of the present invention preferably contains the ethylene/α -olefin copolymer (a) and, if necessary, 1 or more components (B) selected from the group consisting of synthetic oils (C), synthetic oils (D), mineral oils (E), and the like. Further, the lubricating oil composition of the present invention contains the above-mentioned sulfur compound (F). Their content ratios are as described above.

The lubricating oil composition of the present invention may contain known additives such as a pour point depressant, an extreme pressure additive, a friction modifier, an oiliness agent, an antioxidant, an antirust agent, and an anticorrosive agent in an amount of 20 parts by weight or less based on 100 parts by weight of the composition, as necessary.

Such a lubricating oil composition is characterized by exhibiting excellent viscosity characteristics and shear stability in a good balance.

[ pour Point depressant ]

Examples of the pour point depressant include polymers or copolymers of alkyl methacrylate, polymers or copolymers of alkyl acrylate, polymers or copolymers of alkyl fumarate, polymers or copolymers of alkyl maleate, and alkyl aromatic compounds. Among them, a polymethacrylate-based pour point depressant (which is a pour point depressant of a polymer or copolymer containing alkyl methacrylate) is particularly preferable, and the alkyl group of the alkyl methacrylate preferably has 12 to 20 carbon atoms and the content thereof is 0.05 to 2 wt% of the total amount of the composition. These can be obtained from materials commercially available as pour point depressants. Examples of commercially available trade names include Aclube146, Aclube136, manufactured by Sanyo chemical Co., Ltd., Lubran141, Lubran171, manufactured by Toho chemical Co., Ltd.

The above-mentioned components may be used by dissolving or diluting them in mineral oil, ester, or the like. The preferable concentration is 10 to 80%, and more preferably 30 to 70%.

[ extreme pressure additives ]

Examples of the extreme pressure additive include sulfurized olefins, sulfurized fats and oils, thioethers, phosphoric acid esters, phosphorous acid esters, amine salts of phosphoric acid esters, and amine salts of phosphorous acid esters, in addition to the above-mentioned sulfur compounds.

The above-mentioned components may be used by dissolving or diluting them in a solvent or the like containing an ester or the above-mentioned olefin polymer. The preferable concentration is 10 to 80%, and more preferably 30 to 70%.

[ Friction modifier ]

Examples of the friction modifier include organic metal friction modifiers represented by organic molybdenum compounds such as molybdenum dithiophosphate and molybdenum dithiocarbamate.

The above-mentioned components may be used by dissolving or diluting them in an ester or the like. The preferable concentration is 10 to 80%, and more preferably 30 to 70%.

Examples of the oily agent include fatty acids, fatty acid esters, and higher alcohols having an alkyl group having 8 to 22 carbon atoms.

[ antioxidant ]

Specific examples of the antioxidant include: phenol antioxidants such as 2, 6-di-tert-butyl-4-methylphenol; amine antioxidants such as dioctyl diphenylamine; and so on.

In addition, as the defoaming agent, there may be mentioned: silicone defoaming agents such as dimethylsiloxane and silicone dispersion; alcohol, ester based defoamers; and so on.

[ Rust inhibitors ]

Examples of the rust inhibitor include carboxylic acids, carboxylic acid salts, esters, and phosphoric acids. Examples of the anticorrosive agent include benzotriazole and its derivatives, thiazole compounds, and the like.

Examples of the anticorrosive agent include benzotriazole-based, thiadiazole-based, and imidazole-based compounds.

The lubricating oil composition of the present invention is particularly excellent in viscosity characteristics and shear stability, and is excellent in durability and thermal oxidation stability, and is effective as an industrial lubricating oil.

The lubricating oil composition of the present invention has a kinematic viscosity at 40 ℃ of 450 to 51,000mm²In the range of/s. Preferably, the industrial lubricating oil is a lubricating oil composition having a viscosity in the range of ISO-500 to ISO-46,000, and is particularly effective as an open gear oil.

The lubricating oil composition of the present invention can be suitably used as an industrial lubricating oil for various industrial machines and transport machines. Is especially suitable for gear oil. Further, the oil composition can be suitably used as gear oil for construction machinery.

The lubricating oil composition of the present invention is expected to have excellent capability of forming a coating film on a metal surface, to have high lubricating performance, and to be a lubricating oil having excellent transparency even at low temperatures. Although transparency tends to be gradually reduced with continued use, transparency can be used as an index of deterioration and replacement timing. Thus, transparency is also one of the important properties for lubricating oils.

Examples

The present invention will be described below specifically based on examples, and various physical properties in the examples are measured in the following manner.

[ ethylene content ]

The measurement was performed using a japanese electron LA500 nuclear magnetic resonance apparatus in a mixed solvent of o-dichlorobenzene and benzene-d 6 (o-dichlorobenzene/benzene-d 6 ═ 3/1 to 4/1 (volume ratio)) under conditions of 120 ℃, a pulse width of 45 ° and a pulse repetition time of 5.5 seconds. The number of times of measurement is 1000 or more, preferably 10000 or more.

[ B value ]

O-dichlorobenzene/benzene-d₆(4/1[vol/vol％]) As the measurement solvent, under the measurement conditions (100MHz, Japanese Electron ECX400P) of a measurement temperature of 120 ℃, a spectrum width of 250ppm, a pulse repetition time of 5.5 seconds, and a pulse width of 4.7. mu.s (45 ℃ pulse), or a solvent having a spectrum width of 250ppm, a measurement temperature of 120 ℃, a pulse width of 250ppm, a pulse width of 4.7. mu.s (pulse width of 45 ℃ C.),Under measurement conditions (125MHz, Bruker Biospin AVANCEIIICryo-500) in which the pulse repetition time was 5.5 seconds and the pulse width was 5.0. mu.s (45 ℃ pulse)¹³C-NMR spectrum based on the following formula [1]The B value was calculated.

[ mathematical formula 1]

Formula [1]In, P_ERepresents the molar fraction of ethylene content, P_ORepresents the mole fraction of alpha-olefin component, P_OERepresents the mole fraction of ethylene-a-olefin chains in the entire two-unit group chain (dynamic sequences).

[ saturated hydrocarbon content ]

An ECX400 nuclear magnetic resonance apparatus manufactured by Nippon electronic Co., Ltd is used, and deuterated o-dichlorobenzene, deuterated chloroform and deuterated benzene are used as the solvent.

The sample concentration is suitably selected to be 50 to 60mg/0.5mL, and the measurement temperature is suitably selected to be from room temperature to 120 ℃. Observed nucleus is¹H (400MHz), the sequence was a single pulse, the pulse width was 5.12. mu.s (45 ℃ pulse), the repetition time was 7.0 seconds, the cumulative number was 500 or more, and the measurement was performed with 7.10ppm as the reference value of the chemical shift. Peaks derived from 1H or the like of a vinyl group, a methyl group or the like were distributed by a conventional method, and the saturated hydrocarbon content was calculated together with the above results of the ethylene content.

In the polyolefin used in the experimental examples of the present application, a peak derived from an unsaturated carbon-carbon bond was not substantially observed.

[ kinematic viscosity (40 ℃ C., 100 ℃ C.) ]

The determination was made based on ASTM D445. In the present example, the viscosity of the blend oil was adjusted as follows based on each ISO classification.

(1) ISO 460: the kinematic viscosity (40 ℃) of the mixed solution is 460 +/-46 mm²The formulation was carried out in a manner of/s.

(2) ISO 1000: with a kinematic viscosity (40 ℃) of 1000. + -. 100mm²The formulation was carried out in a manner of/s.

(3) ISO 2200: with a kinematic viscosity (40 ℃) of 2200. + -. 220mm²The formulation was carried out in a manner of/s.

(4) ISO 3200: the kinematic viscosity (40 ℃) of the mixed solution is 3200 +/-320 mm²The formulation was carried out in a manner of/s.

(5) ISO 4600: the kinematic viscosity (40 ℃) is 4600 +/-460 mm²The formulation was carried out in a manner of/s.

(6) ISO 6800: the kinematic viscosity (40 ℃) is 6800 +/-680 mm²The formulation was carried out in a manner of/s.

(7) ISO 10000: with a kinematic viscosity (40 ℃) of 10000. + -. 1000mm²The formulation was carried out in a manner of/s.

(8) ISO 22000: the kinematic viscosity (40 ℃) of the mixture is 22000 +/-2200 mm²The formulation was carried out in a manner of/s.

[ viscosity index ]

The viscosity index was measured and calculated by the method described in JIS K2283.

[ molecular weight distribution (Mw/Mn) ]

The following liquid chromatography pump, sampling device, Gel Permeation Chromatography (GPC) column, and differential refractive index detector (RI detector) were connected and subjected to GPC measurement.

A liquid chromatography apparatus: 515HPLC PUMP manufactured by Waters corporation

A sampling device: 717plus Autosampler device manufactured by Waters corporation

Mobile phase: THF (containing stabilizer, grade for liquid chromatography)

A chromatographic column: 1 part of PL company, MIXED-D and 1 part of PL company

Are connected in series.

Sample concentration: 5mg/mL

Flow rate of mobile phase: 1.0 mL/min

Measuring temperature: at normal temperature

Standard curve standard samples: EasiCal PS-1 manufactured by PL corporation

[ shear stability (% reduction in viscosity) ]

The test was conducted by using a KRL shear tester based on CEC-L-45 (CEC: regulatory agency of the European test method for fuel and lubricating oil for automobiles), and the rate of decrease in viscosity at 40 ℃ was evaluated.

The shear stability is a degree of kinematic viscosity loss caused by shearing of a copolymer component in the lubricating oil at a metal sliding portion and cutting of molecular chains.

[ compatibility (solubility of extreme pressure additive) ]

After the blended oil was heated and stirred at 60 ℃, the appearance after 10 days was observed and evaluated according to the following scale.

And A, grading: transparency, score B: slightly cloudy, score C: turbidity

[ analysis of extreme pressure additives (GC/MS method) ]

The structure of the sulfur compound contained in the extreme pressure additive was determined by the so-called GC/MS method using both gas chromatography and mass spectrometer. The measurement conditions are as follows.

The device comprises the following steps: Jms-Q1000GC K9 device manufactured by Japan electronic products

A chromatographic column: DB5MS + DG (internal diameter: 0.25mm, length: 30m)

Column temperature control mode: the temperature was maintained at 40 ℃ for 3 minutes, and the temperature was increased at a rate of 10 ℃/minute until 320 ℃ was reached, and then the temperature was maintained for 29 minutes, and then the process was terminated.

Mobile phase: helium (flow rate: 0.7 ml/min)

Sample injection temperature: 280 ℃ and slit (1/20)

Sample injection amount: 1 μ L (diluting solvent: hexane)

An ionization method: EI (electron ionization), ionization temperature: 200 deg.C

[ thermal Oxidation resistance stability ]

Thermal oxidation stability the degree of varnish after a test time of 72 hours was evaluated in accordance with the method for testing the stability of the acid value of a lubricating oil for an internal combustion engine described in JIS K2514.

[ Components used in the present invention ]

The components of the lubricant bases used in the examples and comparative examples are shown in Table 2.

[ Table 2]

The extreme pressure additives used in the examples and comparative examples are shown below.

HITEC (trademark) -3339 manufactured by AFTON

The sulfur content: 32.6 wt%, phosphorus content: 1.19 wt% (Table of contents)

Di-tert-butyl polysulfide was detected as a sulfur-containing component by the above GC/MS method. In addition, ingredients suggestive of mineral oil are included.

HITEC (trade Mark) 343 manufactured by AFTON

By the above GC/MS method, no peak indicating a sulfur compound having a secondary alkyl group or a tertiary alkyl group was detected.

[ method for polymerizing ethylene-alpha-olefin copolymer (A) ]

[ polymerization example 1]

Into a 1L glass polymerization reactor having an internal volume sufficiently purged with nitrogen, 250mL of heptane was charged, the temperature in the system was raised to 50 ℃, and then ethylene at a flow rate of 25L/hr, propylene at a flow rate of 75L/hr, and hydrogen at a flow rate of 100L/hr were continuously supplied into the polymerization reactor, and stirring was carried out at a stirring rotation speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into a polymerizer, and then 0.023mmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and [ diphenylmethylene (. eta.) ]⁵- (3-n-butylcyclopentadienyl) (. eta.)⁵-2, 7-di-tert-butylfluorenyl group)]A material obtained by premixing 0.00230mmol of zirconium dichloride in toluene for 15 minutes or more was charged into a polymerizer, thereby initiating polymerization. Then, the continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 50 ℃ for 15 minutes. The polymerization was stopped by adding a small amount of isobutanol to the system, and then unreacted monomers were purged. The obtained polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, then washed 3 times with 100mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight at 80 ℃ under reduced pressure to give 1.43g of an ethylene-propylene copolymer. The resulting polymer(Polymer 1) had an ethylene content of 52.4 mol%, Mw of 13,600, Mw/Mn of 1.9, a B value of 1.2 and a kinematic viscosity at 100 ℃ of 2,000mm²/s。

[ polymerization example 2]

Into a 1L glass polymerization reactor having an internal volume sufficiently purged with nitrogen, 250mL of heptane was charged, the temperature in the system was raised to 50 ℃, and then ethylene at a flow rate of 25L/hr, propylene at a flow rate of 75L/hr, and hydrogen at a flow rate of 100L/hr were continuously supplied into the polymerization reactor, and stirring was carried out at a stirring rotation speed of 600 rpm. Subsequently, 0.2mmol of triisobutylaluminum was charged into a polymerization vessel, and then 0.688mmol of MMAO and 0.00230mmol of dimethylsilylbis (indenyl) zirconium dichloride were premixed in toluene for 15 minutes or more to charge into the polymerization vessel, thereby initiating polymerization. Then, the continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 50 ℃ for 15 minutes. The polymerization was stopped by adding a small amount of isobutanol to the system, and then unreacted monomers were purged. The obtained polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, then washed 3 times with 100mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The resulting polymer was dried overnight at 80 ℃ under reduced pressure to give 1.43g of an ethylene-propylene copolymer. The obtained polymer (polymer 2) had an ethylene content of 52.1 mol%, Mw of 13,800, Mw/Mn of 2.0, a B value of 1.2 and a kinematic viscosity at 100 ℃ of 2,000mm²/s。

[ polymerization example 3]

Into a glass polymerization reactor having an internal volume of 1L and sufficiently substituted with nitrogen, 250mL of decane was charged to raise the temperature in the system to 130 ℃ and, thereafter, ethylene at a flow rate of 25L/hr, propylene at a flow rate of 75L/hr and hydrogen at a flow rate of 100L/hr were continuously supplied into the polymerization reactor and stirred at a stirring speed of 600 rpm. Next, 0.2mmol of triisobutylaluminum was charged into a polymerizer, and then MMAO 1.213mmol was reacted with [ [ diphenylmethylene (. eta.) ]⁵- (3-n-butylcyclopentadienyl) (. eta.)⁵-2, 7-di-tert-butylfluorenyl group)]A material obtained by premixing 0.00402mmol of zirconium dichloride in toluene for 15 minutes or more was charged into a polymerizer, thereby initiating polymerization. Then, the continuous supply of ethylene, propylene and hydrogen was continuedFor this, polymerization was carried out at 130 ℃ for 15 minutes. The polymerization was stopped by adding a small amount of isobutanol to the system, and then unreacted monomers were purged. The obtained polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, then washed 3 times with 100mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried overnight under reduced pressure at 80 ℃ to obtain 0.77g of an ethylene-propylene copolymer. The obtained polymer (polymer 3) had an ethylene content of 48.8 mol%, Mw of 4,100, Mw/Mn of 1.7, a B value of 1.2 and a kinematic viscosity at 100 ℃ of 100mm²/s。

[ polymerization example 4]

Into a glass polymerization reactor having an internal volume of 1L and sufficiently substituted with nitrogen, 250mL of decane was charged to raise the temperature in the system to 130 ℃ and, thereafter, ethylene at a flow rate of 25L/hr, propylene at a flow rate of 75L/hr and hydrogen at a flow rate of 100L/hr were continuously supplied into the polymerization reactor and stirred at a stirring speed of 600 rpm. Subsequently, 0.2mmol of triisobutylaluminum was charged into a polymerization vessel, and then a substance obtained by premixing MMAO 1.213mmol and dimethylsilylbis (indenyl) zirconium dichloride 0.00402mmol in toluene for 15 minutes or more was charged into the polymerization vessel, thereby initiating polymerization. Then, the continuous supply of ethylene, propylene and hydrogen was continued, and polymerization was carried out at 130 ℃ for 15 minutes. The polymerization was stopped by adding a small amount of isobutanol to the system, and then unreacted monomers were purged. The obtained polymer solution was washed 3 times with 100mL of 0.2mol/l hydrochloric acid, then washed 3 times with 100mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried overnight under reduced pressure at 80 ℃ to obtain 0.77g of an ethylene-propylene copolymer. The obtained polymer (polymer 4) had an ethylene content of 48.7 mol%, Mw of 4,200, Mw/Mn of 1.8, a B value of 1.2 and a kinematic viscosity at 100 ℃ of 100mm²/s。

(example 1)

93.0% by weight of the polymer 3 (which was an ethylene-propylene copolymer (A)) obtained in polymerization example 3 as a viscosity modifier, 5.0% by weight of a polyol ester (TMTC manufactured by BFS Co., Ltd.) classified into API group (V), and 2.0% by weight of an extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON Co., Ltd.) were blended to adjust the viscosity to ISO 1000. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 2)

The polymer 1(9.5 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (a), the polymer 3(83.5 wt%) obtained in polymerization example 3, the polyol ester (TMTC manufactured by BFS) 5.0 wt% as the synthetic oil (D), and the extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON) 2.0 wt% were blended to adjust the viscosity corresponding to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 3)

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 2, except that the copolymer 1(28.0 wt%) obtained in polymerization example 1 and the polymer 3(65.0 wt%) obtained in polymerization example 3 were used as the ethylene-propylene copolymer (a). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 4)

A viscosity equivalent to ISO6800 was adjusted in the same manner as in example 2, except that the polymer 1(48.0 wt%) obtained in polymerization example 1 and the polymer 3(45.0 wt%) obtained in polymerization example 3 were used as the ethylene-propylene copolymer (a). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 5)

The viscosity of the ethylene-propylene copolymer (a) was adjusted to ISO1000 by blending 1(4.0 wt%) of the polymer obtained in polymerization example 1, 3(84.0 wt%) of the polymer obtained in polymerization example 3, 10.0 wt% of polyalphaolefin (NEXBASE 2006, manufactured by CHEVRON corporation) as the synthetic oil (D), and 2.0 wt% of extreme pressure additive HITEC (trademark) -3339 (manufactured by aft corporation). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 6)

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 5, except that the polymer 1(30.0 wt%) obtained in polymerization example 1 and the polymer 3(58.0 wt%) obtained in polymerization example 3 were used as the ethylene-propylene copolymer (a). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 7)

The polymer 1(10.0 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (a), the polymer 3(73.0 wt%) obtained in polymerization example 3, polyalphaolefin (NEXBASE 2006, manufactured by CHEVRON corporation) 10.0 wt%, polyol ester (TMTC, manufactured by BFS corporation) 5.0 wt%, and extreme pressure additive HITEC (trademark) -3339 (manufactured by aft corporation) 2.0 wt% were blended to adjust the viscosity corresponding to ISO 1000. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 8)

A viscosity equivalent to ISO2200 was adjusted in the same manner as in example 7, except that the polymer 1(30.0 wt%) obtained in polymerization example 1 and the polymer 3(53.0 wt%) obtained in polymerization example 3 were used as the ethylene-propylene copolymer (a). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 9)

The polymer 1(18.0 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (a), high-viscosity polyalphaolefin (DURASYN 180 manufactured by INEOS) 80.0 wt% as the synthetic oil (C), and extreme pressure additive HITEC (trademark) -3339 (manufactured by aft) 2.0 wt% were blended to adjust the viscosity to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 10)

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 9, except that the polymer 1(27.0 wt%) obtained in polymerization example 1 was used as the ethylene-propylene copolymer (a) and 71.0 wt% of high-viscosity polyalphaolefin (DURASYN 180 manufactured by INEOS) was used as the synthetic oil (C). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 11)

The polymer 1(20.0 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (a), high-viscosity polyalphaolefin (DURASYN 180, manufactured by INEOS) 73.0 wt% as the synthetic oil (C), polyol ester (TMTC, manufactured by BFS) 5.0 wt% as the synthetic oil (D), and extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON) 2.0 wt% were blended to adjust the viscosity to correspond to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 12)

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 11, except that the polymer 1(30.0 wt%) obtained in polymerization example 1 was used as the ethylene-propylene copolymer (a) and 63.0 wt% of a high-viscosity polyalphaolefin (DURASYN 180 manufactured by INEOS) was used as the synthetic oil (C). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 13)

The polymer 1(30.0 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (a), 53.0 wt% of high-viscosity polyalphaolefin (DURASYN 180, manufactured by INEOS) as the synthetic oil (C), 10.0 wt% of low-viscosity polyalphaolefin (NEXBASE 2006, manufactured by CHEVRON), 5.0 wt% of polyol ester (TMTC, manufactured by BFS) as the synthetic oil (D), and 2.0 wt% of extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON) were blended to adjust the viscosity to correspond to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 14)

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 13, except that the polymer 1(40.0 wt%) obtained in polymerization example 1 was used as the ethylene-propylene copolymer (a) and 43.0 wt% of a high-viscosity polyalphaolefin (DURASYN 180 manufactured by INEOS) was used as the synthetic oil (C). The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 15)

The polymer 1(20.0 wt%) obtained in polymerization example 1 as the ethylene-propylene copolymer (A), bright stock (N460, manufactured by JX) as the mineral oil (E), and extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON) 2.0 wt% were blended and adjusted to have a viscosity corresponding to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 3.

(example 16)

The ethylene-propylene copolymer (a) was blended in the same manner as in example 15 except that the ethylene-propylene copolymer (a) obtained in polymerization example 1 was used as the polymer 1(40.0 wt%), and 58.0 wt% of bright stock (N460 manufactured by JX corporation) was used as the mineral oil (E), and the viscosity was adjusted to the viscosity equivalent to ISO 4600. The lubricating oil physical properties of the compounded oil are shown in table 3.

[ Table 3]

Comparative example 1

20.0 wt% of polybutene (HV-1900, JX) as a viscosity modifier, 3(78.0 wt%) of the polymer obtained in polymerization example 3 as the ethylene-propylene copolymer (A), and 2.0 wt% of an extreme pressure additive HITEC (trademark) -3339 (manufactured by AFTON) were blended to adjust the viscosity to the viscosity corresponding to ISO 2200. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 2

A viscosity equivalent to ISO6800 was adjusted in the same manner as in comparative example 1, except that 42.0% by weight of polybutene (HV-1900, JX) was used and that polymer 3 (56.0% by weight) obtained in polymerization example 3, which is an ethylene-propylene copolymer (A), was used. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 3

A viscosity equivalent to ISO1000 was adjusted in the same manner as in example 1, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 4

A viscosity equivalent to ISO2200 was adjusted in the same manner as in example 2, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 5

A viscosity equivalent to ISO3200 was adjusted in the same manner as in example 3, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 6

A viscosity equivalent to ISO6800 was adjusted in the same manner as in example 4, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 7

A viscosity equivalent to ISO2200 was adjusted in the same manner as in example 15, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 8

A viscosity equivalent to ISO4600 was adjusted in the same manner as in example 16, except that HITEC (trademark) -3339 (manufactured by aft corporation) as an extreme pressure additive was changed to HITEC (trademark) 343(aft corporation). The results of the compatibility evaluation of the blended oil are shown in table 4.

Comparative example 9

A viscosity equivalent to ISO1000 was prepared by blending the components in the same manner as in example 1, except that the polymer 3 was changed to the polymer 4 obtained in polymerization example 4. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 10

A viscosity corresponding to ISO2200 was prepared in the same manner as in example 2, except that the polymer 1 was changed to the polymer 2 obtained in polymerization example 2 and the polymer 3 was changed to the polymer 4 obtained in polymerization example 4. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 11

A viscosity equivalent to ISO6800 was prepared in the same manner as in example 4, except that the polymer 1 was changed to the polymer 2 obtained in polymerization example 2 and the polymer 3 was changed to the polymer 4 obtained in polymerization example 4. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 12

A viscosity corresponding to ISO2200 was prepared in the same manner as in example 8, except that the polymer 1 was changed to the polymer 2 obtained in polymerization example 2 and the polymer 3 was changed to the polymer 4 obtained in polymerization example 4. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 13

A viscosity equivalent to ISO3200 was prepared in the same manner as in example 14, except that the polymer 1 was changed to the polymer 2 obtained in polymerization example 2. The lubricating oil physical properties of the compounded oil are shown in table 4.

Comparative example 14

A viscosity equivalent to ISO2200 was prepared by blending the components in the same manner as in example 15, except that the polymer 1 was changed to the polymer 2 obtained in polymerization example 2. The lubricating oil physical properties of the compounded oil are shown in table 4.

[ Table 4]

Claims

1. A lubricating oil composition characterized by containing the following (A) and (F) and optionally (G),

(G) a polymer of an alpha-olefin having 3 to 6 carbon atoms,

Wherein the total amount of the lubricating oil composition is 100 parts by weight, the sulfur content is 0.1-5 parts by weight,

(method (. alpha.))

(a) a crosslinked metallocene compound represented by the following formula 1,

(ii) a compound which reacts with the crosslinked metallocene compound to form an ion pair,

[ chemical formula 1]

In the formula 1, R¹、R²、R³、R⁴、R⁵、R⁸、R⁹And R¹²Each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, adjacent groups being optionally linked to each other to form a ring structure,

R⁶、R⁷、R¹⁰and R¹¹Not being hydrogen atoms at the same time;

y is a carbon atom or a silicon atom;

R¹³and R¹⁴Independently is an aryl group;

m is Ti, Zr or Hf;

j is an integer of 1 to 4.

2. The lubricating oil composition according to claim 1, wherein the substituent (R) bonded to the cyclopentadienyl group of the metallocene compound represented by the formula 1¹、R²、R³And R⁴) At least 1 of which is a carbon atomA hydrocarbon group having a number of 4 or more.

3. The lubricating oil composition according to claim 1 or 2, wherein R⁶And R¹¹The same applies to the hydrocarbyl group with 1-20 carbon atoms.

4. The lubricating oil composition according to any one of claims 1 to 3, wherein a substituent (R) bonded to the 3-position of the cyclopentadienyl group of the metallocene compound represented by the formula 1²Or R³) Is a hydrocarbyl group.

5. The lubricating oil composition according to claim 4, wherein a hydrocarbon group (R) bonded to the 3-position of the cyclopentadienyl group of the metallocene compound represented by the formula 1²Or R³) Is n-butyl.

6. The lubricating oil composition according to any one of claims 1 to 5, wherein the substituent (R) bonded to the 2-position and 7-position of the fluorenyl group of the metallocene compound represented by the formula 1⁶And R¹¹) Are all tert-butyl.

7. The lubricating oil composition according to any one of claims 1 to 6, wherein the compound which reacts with the crosslinked metallocene compound to form an ion pair is a compound represented by the following formula 6,

[ chemical formula 2]

In the formula 6, R^e+Is H⁺A carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatriene cation, or a ferrocenium cation with a transition metal, R^f～RⁱEach independently a hydrocarbon group having 1 to 20 carbon atoms.

8. The lubricating oil composition of claim 7, wherein the ammonium cation is a dimethylanilinium cation.

9. The lubricating oil composition of claim 7 or 8, wherein the catalyst system further comprises an organoaluminum compound selected from the group consisting of trimethylaluminum and triisobutylaluminum.

10. The lubricating oil composition according to claim 1, further comprising a component (B) satisfying all of the following requirements (B-1) to (B-3),

(B-2) a viscosity index of 90 or more,

(B-3) a pour point of-10 ℃ or lower.

11. The lubricating oil composition according to claim 10, wherein the component (B) is a synthetic oil (C) satisfying all of the following requirements (C-1) to (C-3),

(C-1) a kinematic viscosity at 100 ℃ of 20 to 120mm²/s，

(C-2) a viscosity index of 120 or more,

(C-3) a pour point of-30 ℃ or lower.

12. The lubricating oil composition according to claim 10, wherein the component (B) is a synthetic oil (D) satisfying all of the following requirements (D-1) to (D-3),

(D-1) kinematic viscosity at 100 ℃ of 3-10 mm²/s，

(D-2) a viscosity index of 120 or more,

(D-3) a pour point of-40 ℃ or lower.

13. The lubricating oil composition according to claim 10, wherein the component (B) is a mineral oil (E) satisfying all of the following requirements (E-1) to (E-3), and the kinematic viscosity at 100 ℃ of the component (E-1) is 3 to 40mm²/s，

(E-2) a viscosity index of 90 or more,

(E-3) a pour point of-10 ℃ or lower.

14. The lubricating oil composition according to claim 11 or 12, wherein the component (C) and/or the component (D) is a synthetic oil containing an alpha-olefin polymer and/or ester compound having 8 to 20 carbon atoms.

15. The lubricating oil composition according to claim 13, wherein the component (E) is 1 or more mineral oils selected from groups (I), (II) and (III) of the API quality classification.

16. The lubricating oil composition according to any one of claims 1 to 9, wherein the component (B) is at least 1 selected from the group consisting of a synthetic oil (C) satisfying all of the following requirements (C-1) to (C-3), a synthetic oil (D) satisfying all of the following requirements (D-1) to (D-3), and a mineral oil (E) satisfying all of the following requirements (E-1) to (E-3),

the content of saturated hydrocarbons is 80 wt% or more based on the total amount of the components (A) to (E),

(C-1) a kinematic viscosity at 100 ℃ of 20 to 120mm²/s，

(C-2) a viscosity index of 120 or more,

(C-3) a pour point of-30 ℃ or lower,

(D-1) kinematic viscosity at 100 ℃ of 3-10 mm²/s，

(D-2) a viscosity index of 120 or more,

(D-3) pour point of-40 ℃ or lower

(E-1) kinematic viscosity at 100 ℃ of 3 to 40mm²/s，

(E-2) a viscosity index of 90 or more,

(E-3) a pour point of-10 ℃ or lower.

17. A lubricating oil composition comprising a liquid random copolymer of ethylene and an alpha-olefin, (F) a sulfur-containing compound wherein at least one of the hydrocarbon groups adjacent to sulfur is a secondary or tertiary hydrocarbon group, and optionally (G) a polymer of an alpha-olefin having 3 to 6 carbon atoms,

(A-3) has a thickness of 30 to 5,000mm²A kinematic viscosity at 100 ℃ in/s,

(A-4) has a pour point of 30 to-45 ℃,

(A-5) has a bromine number of 0.1g/100g or less,

Wherein the total amount of the lubricating oil composition is 100 parts by weight, and the sulfur content is 0.1-5 parts by weight.

18. The lubricating oil composition according to any one of claims 1 to 17, wherein the lubricating oil composition is a gear oil composition.

19. A method for producing a lubricating oil composition, comprising the steps of:

mixing the liquid random copolymer (A), a sulfur-containing compound (F) in which at least one of the hydrocarbon groups adjacent to sulfur is a secondary or tertiary hydrocarbon group, and optionally a polymer of an alpha-olefin having 3 to 6 carbon atoms (G), thereby producing a polymer having a kinematic viscosity at 40 ℃ of 450 to 51,000mm²A step of preparing a lubricating oil composition having a sulfur content of 0.1 to 5 parts by weight,

(method (. alpha.))

(a) a crosslinked metallocene compound represented by the following formula 1,

[ chemical formula 3]

R⁶、R⁷、R¹⁰and R¹¹Not being hydrogen atoms at the same time;

y is a carbon atom or a silicon atom;

R¹³and R¹⁴Independently is an aryl group;

m is Ti, Zr or Hf;

j is an integer of 1 to 4.